Highly Sensitive and Selective Gas Sensors Using P-Type Oxide

Sensors and Actuators B 192 (2014) 607627
Contents lists available at ScienceDirect
Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb
Review
Highly sensitive and selective gas sensors using p-type oxide

semiconductors: Overview
Hyo-Joong Kim, Jong-Heun Lee
Department of Materials Science and Engineering, Korea University, Seoul 136-713, Republic of Korea
a r t i c l e
i n f o
Article history:
Received 24 August 2013
Received in revised form 30 October 2013
Accepted 5 November 2013
Available online 15 November 2013
Keywords:
Gas sensor
p-Type oxide semiconductor
pn junction
Selectivity
Sensitivity
a b s t r a c t
High-performance gas sensors prepared using p-type oxide semiconductors such as NiO, CuO, Cr2 O3 ,
Co3 O4 , and Mn3 O4 were reviewed. The ionized adsorption of oxygen on p-type oxide semiconductors
leads to the formation of hole-accumulation layers (HALs), and conduction occurs mainly along the nearsurface HAL. Thus, the chemoresistive variations of undoped p-type oxide semiconductors are lower than
those induced at the electron-depletion layers of n-type oxide semiconductors. However, highly sensitive
and selective p-type oxide-semiconductor-based gas sensors can be designed either by controlling the
carrier concentration through aliovalent doping or by promoting the sensing reaction of a specic gas
through doping/loading the sensor material with oxide or noble metal catalysts. The junction between
p- and n-type oxide semiconductors fabricated with different contact congurations can provide new
strategies for designing gas sensors. p-Type oxide semiconductors with distinctive surface reactivity
and oxygen adsorption are also advantageous for enhancing gas selectivity, decreasing the humidity
dependence of sensor signals to negligible levels, and improving recovery speed. Accordingly, p-type
oxide semiconductors are excellent materials not only for fabricating highly sensitive and selective gas
sensors but also valuable additives that provide new functionality in gas sensors, which will enable the
development of high-performance gas sensors.
2013 Elsevier B.V. All rights reserved.
Contents
1.
2.
3.
4.
5.
6.
7.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Gas sensing mechanisms of n- and p-type oxide semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
Origin of n- and p-type semiconductivity in oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Formation of electronic coreshell conguration in metal oxides by oxygen adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.
Conduction and gas-sensing mechanisms of n- and p-type oxide semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Highly sensitive gas sensors using p-type oxide semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Morphological design of nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Electronic sensitization by controlling doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.
Chemical sensitization by loading catalyts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Highly selective gas sensors using p-type oxide semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
High-performance gas sensors using oxide pn junctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.
Gas sensors using longitudinal oxide pn junctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.
Gas sensors using nanocomposites between p- and n-type oxide semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.
Gas sensors using 1-dimensional n-type oxide semiconductors decorated with p-type oxide nanoclusters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
High-performance gas sensors using p-type-oxide-semiconductor-loaded n-type oxide semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.1.
Enhancement of recovery speed by loading NiO onto SnO2 hollow spheres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.2.
Humidity-independent gas sensors using NiO-loaded SnO2 nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Biographies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Corresponding author at: Department of Materials Science and Engineering, Korea University, Anam-Dong, Sungbuk-Gu, Seoul 136-713, Republic of Korea.
Tel.: +82 2 3290 3282; fax: +82 2 958 3584.
E-mail address: jongheun@korea.ac.kr (J.-H. Lee).
0925-4005/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.snb.2013.11.005
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H.-J. Kim, J.-H. Lee / Sensors and Actuators B 192 (2014) 607627
1. Introduction
Various oxide semiconductor based gas sensors have been used
to detect harmful and toxic gases [19]. The most representative
sensor materials are SnO2 [10,11] and ZnO [12,13], which exhibit
n-type oxide semiconductivity, and other n-type oxide semiconductors such as TiO2 [14,15], WO3 [16,17], In2 O3 [18,19], and Fe2 O3
[20,21] are being widely explored to nd new functionalities of
chemiresistivity. In contrast, the chemiresistors fabricated using ptype oxide semiconductors such as NiO, CuO, Co3 O4 , Cr2 O3 , and
Mn3 O4 to date have received relatively little attention, and the
related research to fabricate such chemiresistors is still in the early
stages of development. According to the results of a search of web
of knowledge on July 15, 2013 (the keywords used for the search
were the chemical formula of the sensor material and gas sensor*; e.g., SnO2 and gas sensor* were used to search for SnO2
gas sensors), the number of articles found on gas sensors using
p-type oxide semiconductors (i.e., NiO, CuO, Co3 O4 , Cr2 O3 , and
Mn3 O4 ) was only 9.41% of the 8504 articles available on the oxidesemiconductor-based gas sensors (the search results included the
aforementioned p-type oxide semiconductor gas sensors and ntype oxide semiconductor gas sensors fabricated using SnO2 , ZnO,
TiO2 , WO3 , In2 O3 , and Fe2 O3 ) (Fig. 1). Table 1 summarizes the
properties of the gas sensors fabricated using the various p-type
oxide semiconductors such as NiO, CuO, Co3 O4 , Cr2 O3 , Mn3 O4 , and
LaOClNiO, as surveyed in the literature [2254]. The gas sensors
were used to detect C2 H5 OH, HCHO, CO, NH3 , (CH3 )3 N (trimethylamine), H2 , H2 S, C6 H4 (CH3 )2 (xylene), and C6 H5 (CH3 ) (toluene)
whose concentrations were in the range 11000 ppm.
The markedly different gas-sensing characteristics of n- and ptype oxide semiconductors should be understood in the context of
the receptor functions, conduction paths, and gas-sensing mechanisms of these two types of materials with different majority
charge carriers: (1) the formation of an electron-depletion layer
(EDL) in n-type oxide semiconductors or a hole-accumulation layer
(HAL) in p-type oxide semiconductors by the adsorption of oxygen with negative charge; (2) conduction through the serial paths
(i.e., the semiconducting particle cores and resistive interparticle
contacts) in n-type oxide semiconductors or conduction through
the parallel paths (i.e., the resistive particle cores and semiconducting near-surface regions) in p-type oxide semiconductors; and
(3) chemoresistive variation at the interparticle contacts in n-type
oxide semiconductors or at the near-surface regions in p-type oxide
semiconductors.
Compared to n-type oxide semiconductor gas sensors, p-type
oxide semiconductor gas sensors exhibit not only shortcomings
but also promising potentials for practical applications. Hbner
et al. [55] suggested that the response of a p-type oxide semiconductor gas sensor to a given gas was equal to the square root
of that of an n-type oxide semiconductor gas sensor to the same
gas when the morphological congurations of both sensor materials were identical. This nding indicates that the responses of
p-type oxide semiconductor sensors to gases should be enhanced
in order to more accurately detect trace concentrations of various
analyte gases. Nevertheless, the crucial importance of p-type oxide
semiconductors as chemiresistive materials should not be underestimated considering that most p-type oxide semiconductors such
as NiO, CuO, Cr2 O3 , Co3 O4 , and Mn3 O4 have been extensively used
as good catalysts [5659] to promote selective oxidation of various
volatile organic compounds (VOCs). From this perspective, p-type
oxide semiconductors are promising material platforms for developing the new functionalities of chemiresistors. Moreover, the pn
junction between oxide semiconductor materials can also be used
to alter the gas-sensing characteristics of gas sensors by varying the
electrical properties near heterointerfaces [60]. Further, the distinctive oxygen adsorption of p-type oxide semiconductors may
be used to design high-performance gas sensors that show low

humidity dependence and rapid recovery kinetics [61,62].
Accordingly, p-type oxide semiconductors can provide a variety of new functionalities in oxide chemiresistors. However, to the
best of our knowledge, there have been no comprehensive reviews
previously published on gas sensors using p-type oxide semiconductors as sensing or additive materials. In this study, we review
various high-performance gas sensors using p-type oxide semiconductors. As shown in Fig. 2, our review places special focus
on (1) the gas-sensing mechanism of p-type oxide semiconductors, (2) new strategies to enhance the response of p-type oxide
semiconductor sensors to gases through electronic and chemical
sensitization, (3) highly selective gas sensors fabricated using ptype oxide semiconductors, (4) various gas sensors fabricated using
oxide pn junctions, and (5) designing reliable n-type oxide semiconductor gas sensors by loading p-type oxide additives.
2. Gas sensing mechanisms of n- and p-type oxide
semiconductors
2.1. Origin of n- and p-type semiconductivity in oxides
The major charge carriers in Si-based semiconductors can be
manipulated by proper doping of donor or acceptors [63]. In
contrast, the major charge carriers in wide-bandgap oxide semiconductors are determined either by doping aliovalent cations [64] or
by oxygen nonstoichiometry [65]. For example, undoped oxygendecient SnO2 shows n-type semiconductivity since the formation
of oxygen vacancies accompanies the generation of electrons [66].
The p-type semiconductivity of undoped NiO can be explained by
the deciency of metal ions in the material [67]. The concentration
of charge carriers in materials used for the gas sensor applications
may be changed or tuned to the proper range at the operation
temperature in order to achieve high responses to gases and/or
to control the resistance of the sensor material so that the sensor system may use simple measurement circuit. Since the oxygen
nonstoichiometry cannot be varied at xed sensing temperature
and ambient atmosphere, the doping of higher and lower valency
cations may be used to control the charge carrier concentration of
gas sensing materials [68,69].
2.2. Formation of electronic coreshell conguration in metal
oxides by oxygen adsorption
At 100500 C, oxygen molecules adsorb onto the surfaces of
n-type oxide semiconductors such as SnO2 and ZnO and ionize
into species such as O2 , O , and O2 by taking electrons near the
surfaces of the semiconductors [5,6]. In general, the ionosorption
species of O2 , O , and O2 are known to be dominant at <150 C,
between 150 and 400 C, and at >400 C, respectively [6]. This leads
to the formation of an electronic coreshell conguration (Fig. 3a);
that is, an n-type semiconducting region at the cores of particles and
resistive EDL at the shells of the particles. The adsorption of oxygen
anions in p-type oxide semiconductors forms the HAL near the surface of the material because of the electrostatic interaction between
the oppositely charges species (Fig. 3b), which again establishes the
electronic coreshell conguration; that is, the insulating region at
the cores of particles and semiconducting HALs near the surface of
the particles.
The majority of charge carriers near the surfaces of oxide semiconductors and the number of oxygen anions on the surfaces of
oxide semiconductors are signicantly different in p- and n-type
oxide semiconductors. Iwamoto et al. [70] used temperatureprogrammed desorption (TPD) after oxygen had been adsorbed
under dened conditions onto various materials to investigate the
609
Fig. 1. Studies on n- and p-type oxide semiconductor gas sensors (internet search of Web of Knowledge on July 15, 2013).
amount of oxygen adsorbed in 16 metal oxides by measuring the

total amount of oxygen desorbed below 560 C (V560 ) (Fig. 4). Note
that the V560 values of p-type oxide semiconductors such as CuO,
Co3 O4 , NiO, MnO2 , and Cr2 O3 are markedly larger than those of
n-type oxide semiconductors such as Fe2 O3 , SnO2 , ZnO, and TiO2 .
Among n-type oxide semiconductors, the transition metal oxides,
Fe2 O3 with multi-valency characteristics showed the highest V560
value. This nding indicates that a large amount of oxygen is
adsorbed in transition metal oxides whose oxidation states may
vary. Although the V560 values for a few of the oxides slightly deviated from the overall correlation, V560 tended to decrease with
increasing the heat of formation of oxides per gram of oxygen atoms
(Hf ) (Fig. 4). The low stability (i.e., low Hf ) of multivalent
transition metal oxides can lead to increased oxygen adsorption in
the materials. For example, the charge compensation through the
oxidation of Ni2+ to Ni3+ reportedly promotes and facilitates the
adsorption of oxygen onto NiO [71,72]. Thus, the large amount of
oxygen adsorbed in p-type transition metal oxides can be understood in relation to the low stability of oxides associated with redox
reactions promoted by variable oxidation states. The distinctive
surface characteristics of p-type oxide semiconductors can show
various reactivities to reducing gases and dissimilar interactions
with humidity and thus can provide different gas-detection characteristics.
Table 1
Various p-type metal oxide semiconductor-based gas sensors surveyed in literature [2254].
Sensor material
Target gas
Structures
Particle size (nm)
Gas concentration
(ppm)
Sensing temp. ( C)
Refs.
NiO
C2 H5 OH
Nanoowers
Nanotubes
Nanowires
Hemispheres
Hollow spheres
Porous thin lms
Thin lms
Hierarchical NSsa
Nanowires
Dendritic wires
Nanowires
200800
20200
150400
[2226]
10002000
5100
240350
[2729]
3500
150200
20
50
[30]
[31,32]
230
500
180260
RT (room
temperature)
350
10010,000
501000
RT240
[3336]
3000
1001000
200300
[37,38]
10015,000
0.1100
RT300
[3943]
100
10,000
RT
[44]
206000
10500
1352000
[4547]
430560
20
1001000
100200
200
200
[48]
[46]
HCHO
CO
NH3
(CH3 )3 N
CuO
C2 H5 OH
H2
H2 S
NH3
Co3 O4
C2 H5 OH
HCHO
C6 H4 (CH3 )2
Nanoparticles
Nanorods
Hierarchical NSs
Thin lm
Urchin-like NSs
Porous thin lm
Nanowires
Nanorods
Nanosheets
Hollow spheres
Thin lm
Nanowires
Nanocubes
Microspheres
Nanocrystals
Nanocubes
[25]
20621
2501000
300450
[4951]
H2 S
C6 H4 (CH3 )
Mesoporous NSs
Thin lm
Thin lm
Microspheres
621
1200
1000
200
170
300450
[51]
[52]
Mn3 O4
C2 H5 OH
Nanowires
50
2.5100
300450
[53]
LaOClNiO
C2 H5 OH
Nanobers
1000
100
400
[54]
Cr2 O3
C2 H5 OH
NSs: nanostructures.
610
Fig. 2. High-performance gas sensors fabricated using p-type metal oxide semiconductors.
2.3. Conduction and gas-sensing mechanisms of n- and p-type

oxide semiconductors
Although both n- and p-type oxide semiconductors establish
electrical coreshell layers by adsorbing oxygen, they exhibit
signicantly different conduction behaviors. The sensor resistance
of n-type oxide semiconductors is mainly determined by the
resistive shell-to-shell contacts formed between the particles in
oxide semiconductors (Fig. 5a). Thus, equivalent circuits of n-type
semiconductor gas sensors can be explained as serial connections
between semiconducting cores (Rcore ) and resistive interparticle
contacts (Rshell ) (Fig. 5b). When an n-type semiconductor gas
sensor is exposed to a reducing gas (e.g., CO), ionized oxygen
anions (i.e., O2 , O , and O2 ) are used to oxidize the reducing
gas, and the remanent electrons are injected into semiconducting
core, which decreases the sensor resistance proportional to the

concentration of reducing analyte gas. Accordingly, the high
responses to trace concentrations of various reducing gases in
n-type oxide semiconductors reported in the literature [7377]
are attributed to the signicant variation in the chemiresistivity at
the interparticle contacts.
In stark contrast, the conduction in p-type oxide semiconductors can be explained by the competition between parallel
paths across the wide, resistive core (Rcore ) and along the narrow,
p-semiconducting shell (Rshell ) regions. The detailed conduction
model and energy band diagram of p-type oxide semiconductor gas
sensors are well explained by Barsan et al. [78] (Fig. 6a). In Fig. 6a,
the B region represents the semiconductor graingrain contacts,
while A and C regions show electrode (metal)semiconductor
contacts. Under this conguration, the electrons injected into the
Fig. 3. Formation of electronic coreshell structures in (a) n-type and (b) p-type oxide semiconductors.
Fig. 4. Correlation between amount of desorbed oxygen (V560 ) and heat of formation
of oxides per gram of oxygen atom (Hf ).
Reproduced with permission from Ref. [70].
material through the oxidation reaction between the reducing gas

and the oxygen anions on the surface of the oxide semiconductors
decreases the concentration of holes in the shell layer, which in
turn increases the sensor resistance (Fig. 6b and c). However, if
one assumes that the oxide semiconductor particles are larger
than twice the thickness of the HAL (tHAL ), the slight change in
the concentration of holes in the shell layer due to electronhole
recombination will not lead to signicant variation in the chemiresistivity at the interparticle contacts, which is feasible considering
that the conduction in p-type oxide semiconductors mainly occurs
along semiconducting shells. Hbner et al. [55] reported that
the gas response of p-type-oxide-semiconductor-based gas sensors (Sp ) (i.e., the relative change in sensor conductance/resistance
when a sensor is exposed to a gas) is equal to the square root of that
of n-type oxide semiconductor-based gas sensors (Sn ) whose morphologies are identical to the p-type-oxide-semiconductor-based
gas sensors. The relation is given as follows:
Sp =
Sn .
(1)
This insightful equation clearly shows that designing highly

sensitive gas sensors using p-type oxide semiconductors is challenging. The C2 H5 OH-detection characteristics of n- and p-type
611
oxide semiconductors were the most abundant in the literature.

Accordingly, we plotted the responses (Ra /Rg for n-type oxide
semiconductors, Rg /Ra for p-type oxide semiconductors, Ra : resistance in air, Rg : resistance in gas) of various n- and p-type oxide
semiconductors for various concentrations of C2 H5 OH in Fig. 7
[2225,27,30,3336,4548,79100] to demonstrate that it is challenging to design highly sensitive gas sensors with p-type oxide
semiconductors. Even if we take into account some variation in
gas responses due to the variation in the morphology of the oxide
semiconductor particles and the temperatures at which the concentrations of C2 H5 OH were measured, the graph clearly shows
that the gas responses of n-type oxide semiconductors tend to be
signicantly higher than those of p-type oxide semiconductors,
which is consistent with Eq. (1).
The resistance of p-type oxide semiconductor is known to
decrease upon exposure to oxidizing gases such as NO2 and O3 .
This is explained by the increase of hole concentration in the shell
layer due to the ionosorption of oxidizing gas. However, chemoresistive variation of p-type oxide semiconductors to oxidizing gas
seems to be also not high considering the gas sensing mechanism.
This is supported by the literature data [23,101104] that pure NiO
and CuO sensor showed relatively low responses (Ra /Rg = 1.07.5)
to 10100 ppm NO2 .
3. Highly sensitive gas sensors using p-type oxide
semiconductors
It is essential to enhance the gas response of p-type oxide semiconductors in order to use them in practical sensor applications.
The gas response of p-type oxide semiconductor gas sensors can
be enhanced by (1) tuning the morphology of the nanostructures
in the oxide semiconductors, (2) doping with additives to electronically sensitize the oxide semiconductor, or (3) loading noble
metals or metal oxide catalysts to chemically sensitize the oxide
semiconductors.
3.1. Morphological design of nanostructures
The sizes of nanostructures in n-type oxide semiconductors
determine the degree of electron depletion [105108], while
the morphologies, assembled conguration, and agglomeration
of nanostructures dominate the chemiresistivity of the interparticle contacts and the gas accessibility [109112]. Thus, small
nanostructures whose congurations are readily accessible to gas
molecules are advantageous to design highly sensitive n-type oxide
Fig. 5. Gas-sensing mechanism and equivalent circuit of n-type oxide semiconductors.
612
Fig. 6. (a) Sensing layer of p-type oxide semiconductor gas sensors: simplied depiction of the relevant sensing layer elements (low) (A, C: metalsemiconductor contact,
B: semiconductor graingrain contact), relevant energy band diagram (upper) suggested by Barsan et al. Reproduced with permission from [78]. (b, c) Simplied gas sensing
mechanism and equivalent circuit of p-type oxide semiconductors.
semiconductor gas sensors. The gas responses of p-type oxide

semiconductors also depend upon the size of the nanostructures
because the chemiresistive variation of oxide semiconductors is the
results of the interaction between an analyte gas and the surfaces
of oxide semiconductors.
The gas responses of n-type oxide semiconductors dramatically
increase to a very high level with decreasing size of the metal
oxide semiconductor particles to smaller than twice the thickness
of the EDL (tEDL ) [105107]. However, the dependence of the
gas responses of p-type oxide semiconductors on particle size
has not yet been well-established. The gas responses for large
and small p-type metal oxide semiconductor particles can be
semiquantitatively compared using the simplied cube model
that Barsan et al. suggested (Fig. 8) [78]. The gas responses of
a large or small cube whose edges are 100 or 20 nm long were

calculated. In both large and small cubes, the tHAL value (X0 in
Fig. 8a) was assumed to be 5 nm. The cube whose edge length (D)
is 100 nm can be divided into 3 parts according to the conduction
path and resistivity: (1) two thin p-semiconducting slabs (whose
dimensions are 100 nm 100 nm 5 nm) on the exterior (parts
1 and 4; resistance: R1 and R4 ); (2) thin semiconducting layers
surrounding the insulating cube (i.e., two slabs whose dimensions
are 100 nm 90 nm 5 nm and two slabs whose dimensions
are 90 nm 90 nm 5 nm) (part 2; resistance: R2 ); and (3) one
insulating cube (whose dimensions are 90 nm 90 nm 90 nm) at
the central region (part 3; resistance: R3 ) (Fig. 8b). We assumed
core /shellair = 10 and shellgas /shellair = 4 (where core represents the resistivity of the resistive core, shellair represents the
613
Fig. 7. (a) Responses of n- and p-type oxide semiconductor gas sensors to C2 H5 OH reported in literature [7995 (N1N17), 2225 (P1P4), 27 (P5), 30 (P6), 3336 (P7P10),
4548 (P11P14), and 9698 (P15P17)] and (b) enhanced response of Fe-doped NiO hierarchical nanostructure to C2 H5 OH gas. Response was enhanced by electronically
sensitizing nanostructures with Fe doping [99,100].
resistivity of the p-semiconducting shell in air, and shellgas represents the resistivity of the p-semiconducting shell under the gas
atmosphere), the gas response (Rg /Ra ) of the large cube (D: 100 nm)
was calculated as 2.618. The gas response (Rg /Ra ) of the small cube
(D: 20 nm) was similarly calculated as 3.801. When the large cube is
markedly thicker than 2tHAL (or 2X0 in Fig. 8a), the entire resistance
of the sensor depends less upon the variation in the resistance of
shell layer because the conduction along the resistive core region,
whose cross-sectional area is very wide, will dominate. The gas
response will accordingly remain low unless the chemiresistive
variation at the shell region is very high. In contrast, when the
length of the edge of the large cube is comparable to or slightly
larger than 2tHAL , the chemiresistive variation at the shell layer contributes more to the change in the resistance of the sensor, which
leads to the higher gas response. From this perspective, decreasing
the size of metal oxide semiconductor particles also enhances the
response of p-type oxide semiconductor gas sensors to various
gases. Note that the gas-detection characteristics of p-type oxide
semiconductor gas sensors and their dependence on particle size
can be tuned by varying tHAL /D, core /shellair , coregas /shellair , and
so on. It should be noted that a new formula for estimating gas
response is necessary when the particle size is smaller than 2tHAL .
The interparticle contact area is also a key parameter that can
affect the gas response of p-type oxide semiconductors. We electrospun and subsequently heated Co3 O4 at 600 C to prepare a
conguration of connected Co3 O4 nanobers [113] whose crystallite sizes were 105.8 42.7 nm. The Co3 O4 nanobers were
ultrasonically treated for 1 h to completely disconnect and break
them apart into nanoparticles. The gas response of the ultrasonically treated Co3 O4 nanoparticles to 100 ppm C2 H5 OH at 301 C was
Rg /Ra = 2.71, signicantly lower than that (Rg /Ra = 45.3) of the connected conguration of Co3 O4 nanobers whose crystallite size was
identical. Barsan et al. [78] suggested that the gas response of p-type
oxide semiconductors whose grains were larger than the Debye
length (LD ) could increase with increasing diameter of the neck
between two particles when the grain size is constant. Therefore,
the marked decrease in gas response of the ultrasonically treated
Co3 O4 nanobers was attributed to the decrease in the contact
Fig. 8. Simplied model of p-type metal oxide grains, used for the calculation of the grain resistance: (a) the cubic grain model; (b) sketch of the electrical connection between
the different grain parts; and (c) the corresponding DC equivalent circuit of the grain.
Reproduced with permission from [78].
614
Table 2
Effect of morphology of particles (Sspecial morphology /Sanother morphology ) on gas response of p-type metal oxide semiconductor-based gas sensors [23,26,27,37,41,48,114116].
Gas concentration
(ppm)
Sensor
material
Target gas
Morphology
Sensing
temperature ( C)
NiO
C2 H5 OH
Hemispheres
300
100
NiO
C2 H5 OH
Nanotubes
250
50
NiO
C4 H9 OH
Hollow spheres
350
500
CuO
H2
Hierarchical NSs
200
100
CuO
H2 S
Hierarchical NSs
190
Co3 O4
HCHO
Mesocrystals
200
500
Co3 O4
CO
Nanorods
250
50
CO3 O4
C2 H5 OH
Nanosheets
400
100
Cr2 O3
C2 H5 OH
Nanobers
400
1000
Response
(S = Rg /Ra )
Morphological
effect
Refs.
SHemisphers = 4.2
SThinlm = 2.7
SNanotubes = 4.2
SNanobers = 1.4
SHollow spheres = 2.55
SNanoparticles = 1.73
SHierarchical = 5.8
SNanorods = 3.4
SHierarchical = 4.5
SSolid spheres = 3.2
SMesocrystal = 3.15
SNanorods = 6.5
SNanosheets = 57.7
SNanobers = 1.72
1.5
[23]
[26]
1.47
[27]
1.70
[37]
1.40
[41]
2.03
[48]
2.95
[114]
10.5
1.53
[115]
[116]
area between particles, indicating that the interparticle connection

conguration is an important factor to consider when designing
highly sensitive p-type oxide semiconductor gas sensors.
The effect of morphology on the variation in the gas response
of the p-type oxide semiconductors surveyed in the literature is
summarized in Table 2 [23,26,27,37,41,48,114116]. The variations
in the morphology of the nanostructures include the differences
in size, interparticle contact, and agglomeration. Thus, it remains
difcult to elucidate in detail the effect of each variable on the
gas-detection characteristics of oxide semiconductors. However, it
is obvious that morphology is an important parameter for tuning
the gas responses of oxide semiconductors. Although the response
ratios of nanostructures with two different morphologies in the
NiO, CuO, Co3 O4 , and Cr2 O3 oxide semiconductors surveyed in the
literature are generally low (i.e., in the range 1.42.95) although
one a report showed relatively high ratio (10.5) [115]. Note that
the enhanced gas response achieved using well-dened or welldispersed nanostructures in p-type oxide semiconductor sensors
is lower than that achieved using the n-type oxide semiconductor
sensors, which can be attributed to the inherently low gas response
of p-type oxide semiconductor sensors because of their distinctive
gas-sensing mechanism.
3.2. Electronic sensitization by controlling doping
The chemiresistive variation in oxide semiconductor gas
sensors emanates from the change in the charge carrier conduction in oxide semiconductors upon reaction with analyte
gas. Thus, the concentration of charge carriers and the conguration of the electrical coreshell are key parameters for
tuning the gas responses of oxide semiconductors. Enhancement
of gas response by tuning the concentration of charge carriers
is referred to as electronic sensitization [117]. To date, there
have been many reports on the use of acceptor doping [118,119]
to decrease the concentrations of electrons throughout entire
semiconductors or to decrease the concentrations of electrons
adjacent to second phases [120] in order to make n-type oxide
semiconductors more sensitive to reducing gases. Designing highly
sensitive p-type oxide semiconductor gas sensors by tuning the
concentration of holes has scarcely been reported. Nevertheless,
electronically sensitizing p-type oxide semiconductors is an important method of developing practical p-type oxide semiconductor
gas sensor applications, especially considering that achieving high
gas response in p-type oxide semiconductors is challenging even
when very small nanostructures are used, because of the distinctive

gas-sensing mechanism of p-type oxide semiconductors.
The present authors [99] have previously reported that doping p-type NiO with Fe can signicantly enhance the gas response
of p-type NiO. We prepared hollow NiO spheres (shell thickness:
12 nm; diameter: 300 nm) doped with 0.3 at% Fe by coating
thin layers of Fe precursors onto Ni template spheres, partially
oxidizing the outer Ni spheres into NiO, dissolving the metallic
Ni core in dilute HCl, and heating the hollow spheres at 600 C
(Fig. 9ac). To study the effect of Fe doping on the gas-detection
characteristics of NiO we also prepared for comparison undoped
NiO hollow spheres by similar processes of coating Ni precursors,
heating the spheres, and subsequently removing the Ni core templates. Doping the sensor with Fe increased the response (Rg /Ra ) of
the sensor to 100 ppm C2 H5 OH at 350 C from 5.5 to 172.5 (Fig. 9d
and e).
Motivated by the Fe-doping-induced 31.4-fold increase in the
gas response of the sensor, we then used electrospinning to prepare
pure NiO nanobers and NiO nanobers doped with Fe concentrations in the range 0.1813.2 at% in order to investigate how Fe
doping enhanced the gas response of NiO [100]. The gas responses
(Rg /Ra ) of the sensors to 100 ppm C2 H5 OH increased to 115.6 times
with increasing concentration of Fe dopant to 3.04 at% (Fig. 10).
The change in the particle size due to Fe doping could be excluded
from the main reason for the sensitization from the dramatically
different gas responses of pure NiO bers and 1.02 at% Fe-doped
NiO nanobers in spite of similar particle sizes and BET surface area. Note that electrons are generated to compensate for
substituting Fe3+ ions into Ni2+ sites, which can decrease the concentration of holes in NiO through the recombination reaction as
follows:
2NiO
Fe2 O3 2FeNi + 2OX

O+
1
O2 (g) + 2e .
2
(2)
This incorporation reaction clearly explains the increase in sensor resistance with increasing concentration of Fe dopant. The
gas response of the sensor also showed a similar increase with
increasing concentration of Fe dopant (Fig. 10). This nding strongly
suggests that the gas response of the sensor is correlated with
the concentration of charge carriers in the material. That is, the
Fe-doped NiO (which contained a lower concentration of holes
in the HAL) was more sensitive to the same number of electrons
injected into the sensor from the reaction with analyte gas than the
undoped NiO (which contained a higher concentration of holes in
615
Fig. 9. (a, b) TEM images and (c) element-mapping image of 0.3 at% Fe-doped NiO hollow spheres and (d, e) C2 H5 OH-detection characteristics of pure and 0.3 at% Fe-doped
NiO hollow spheres measured at 350 C, according to Ref. [99].
the HAL). The gas responses of the 3.04 at% Fe-doped NiO nanobers
and the 0.3 at% Fe-doped hollow NiO spheres to 100 ppm C2 H5 OH
were (Rg /Ra = 245.0) [100] and (Rg /Ra = 172.5) [99], respectively,
and are two of the highest gas responses ever reported for p-type
oxide semiconductors (Fig. 7b). Moreover, the 3.04 at% Fe-doped
NiO nanobers showed a substantial response of Rg /Ra = 3.35 even
to 0.05 ppm C2 H5 OH. This result demonstrates that p-type oxide
semiconductors can be also used to develop practical sensor
applications for detecting the ppb-level concentration of analyte
gases.
The present authors [104] reported the doping of 2.2 at% of
Cr to CuO nanostructures by solvothermal reaction signicantly
increases the responses to 100 ppm NO2 from Ra /Rg = 7.5 to
Ra /Rg = 134.2 and the Ra value from 0.92 M to 20.40 M at 250 C.
The marked increase in the gas response can be explained by the
increase in sensor resistance due to doping the CuO with trivalent
Cr, indicating that the electronic sensitization is also a valid and
effective approach to detect oxidizing gas as well as reducing gases
in a highly sensitive manner.
These results clearly show that electronic sensitization is a powerful tool that can be used to design highly sensitive p-type oxide
semiconductor gas sensors. Most p-type oxide semiconductors
such as Co3 O4 , NiO, Cr2 O3 , Mn3 O4 , and CuO are oxides of d-block
transition metals and thus exhibit variable oxidation states. Accordingly, aliovalent doping should be carefully designed taking into
account the coexistence of multivalent ions, the change in the radii
of the host ions with the change in the valence of the ions, and the
solubility limit of dopant in the oxide semiconductor matrix.
3.3. Chemical sensitization by loading catalyts
The gas response of p-type oxide semiconductors also increases
by loading noble metals. The relevant results in the literature are
summarized in Table 3 [24,30,121124]. Wang et al. previously
reported that decorating PdO onto ring-like NiO nanostructures
enhanced the response (Rg /Ra ) of the sensor to 20 ppm CO from
8.2 to 27.5 [30]. They [122] also reported that the response of
hierarchical hollow NiO nanostructures to CH3 COCH3 can be
616
Fig. 10. Gas response ((Rg Ra )/Ra ) and sensor resistance in air (Ra ) for pure and Fe-doped NiO nanobers measured at (a-1, a-2) 350 C, (b-1, b-2) 375 C, (c-1, c-2) 400 C,
(d-1, d-2) 425 C, (e-1, e-2) 450 C, and (g-1, g-2) 500 C.
Table 3
Effect of noble metal catalyst loading on gas-sensing characteristics of p-type MOSs surveyed in literature [24,30,121124].
Sensor materials
Target gas
Morphology
PdONiO
CO
Hierarchical NSsa
PtNiOPt
C2 H5 OH
AuNiO
Sensing temperature
( C)
Gas concentration
(ppm)
Nanobers
180
260
400
100
H2
Thin lms
200
300
AuNiO
CH3 COCH3
Microspheres
240
50
PtNiO
C2 H5 OH
Nanotubes
200
100
Au/PtCuO
HCHO
Nanoribbons
200
500
20
Response
(S = Rg /Ra )
SPdO-NiO = 27.5
SNiO = 8.2
SPt-NiO-Pt = 11.7
SNiO = 1.69
SAu-NiO = 1.3
SNiO = 1.06
SAu-NiO = 10.1
SNiO = 1.5
SPt-NiO = 20.8
SNiO = 2.06
SPt-CuO = 7.9
SAu-CuO = 6.2
SCuO = 4.5
SCatalyst-loaded /SPure
Refs.
3.35
[24]
6.92
[30]
1.22
[121]
6.70
[122]
10.1
[123]
Pt: 1.75
Au: 1.38
[124]
enhanced to 6.7 times by loading the nanostructures with Au

nanoparticles. One of the present authors [24] previously demonstrated that loading Pt nanoparticles onto both the inner and
outer walls of thin NiO tubes can enhance the response (Rg /Ra ) to
100 ppm C2 H5 OH from 1.69 to 11.7. It is noteworthy that in all three
studies, the selectivity of the oxide semiconductor sensors to CO,
CH3 COCH3 , and C2 H5 OH was also enhanced [24,30,122], indicating
the chemical sensitization of noble metals or noble metal oxides.
However, only a limited number of studies have reported the effects
of noble metal catalysts on the gas-detection characteristics of
p-type oxide semiconductors. Therefore, more investigations are
needed in order to elucidate the effects.
4. Highly selective gas sensors using p-type oxide
semiconductors
A range of reducing gases can similarly react with oxygen anions
on the surface of oxide semiconductors, which often hinders distinguishing among various gases. The gas selectivities of various
n- and p-type oxide semiconductor sensors have been reported
during the last 5 years [2225,30,35,36,45,48,8185,125131]. The
ratio between the response to a target gas and the highest response
to an interfering gas (Starget /Sinterference ) was calculated as a measure
of gas selectivity. The selective detection of C2 H5 OH has frequently
been reported for both n- and p-type oxide semiconductors
[22,24,35,36,45,8385,125,126]. However, Starget /Sinterference for
most sensors ranged from 1 to 4 when the target gas was not
C2 H5 OH [14,23,25,30,48,76,81,82,120,127131] (Fig. 11). This
means that the design of oxide semiconductor gas sensors to
selectively detect specic gas except C2 H5 OH remains challenging.
Thus far, many strategies including promoting specic gassensing reactions by catalyst loading [132], varying sensing
temperature [133], controlling the size and number of nanopores
and mesopores in oxide semiconductor materials [134], tuning the
acidity or basicity of sensor materials [135,136], and using catalytic
ltering layers [137] have previously been suggested to enhance
the gas selectivity of n-type oxide semiconductor gas sensors. It is
noteworthy that most p-type oxide semiconductors such as NiO,
CuO, Co3 O4 , Cr2 O3 , and Mn3 O4 are oxides of transition metals,
which exhibit various oxidation states because of the electrons
in the d shell of the metal atom. These materials generally show
distinctive catalytic activities that promote the oxidation of volatile
617
Table 4
Catalytic activation of various p-type oxides surveyed in literature toward various gases [138148].
Catalyst
Catalytic conversion
Temperature ( C)
Refs.
SiO2 NiO nanoparticles

Porous NiO nanoowers
NiO
Mesoporous CuOFe2 O3
Mesoporous CuO/RuO2
CuOCeO2 nanoplates
Porous Co3 O4 nanoowers
Co3 O4 nanorods
Mesoporous Cr2 O3
Mesoporous Cr2 O3
Porous Cr2 O3
C2 H6
C6 H4 (CH3 )
CO
CO
NH3
C6 H6
C6 H4 (CH3 )
NH3
C6 H4 (CH3 ), CH3 CHO
C6 H4 (CH3 )
NO
240420
130310
250500
40120
50300
120240
120300
150
RT85
50350
500600
[138]
[139]
[140]
[141]
[142]
[143]
[144]
[145]
[146]
[147]
[148]
Fig. 11. The ratio between the response to non-ethanol target gas and the
highest response to interference gas in the literature [23,25,30,48,76,81,82,117,
119,127131].
Fig. 13. Gas responses (Ra /Rg or Rg /Ra ) of (a) pure CuO and (b) 2.2 at% Cr-doped
CuO nanostructures to 100 ppm NO2 , C2 H5 OH, NH3 , trimethylamine, C3 H8 , and CO
measured at 250 C, according to Ref. [104].
organic compounds such as CO, NH3 , C2 H6 , CH3 CHO, C6 H6 , and

C6 H4 (CH3 ) because p-type oxide semiconductors show an afnity
with oxygen and multivalent characteristics (Table 4) [138148].
This means that p-type oxide semiconductors are promising platform for developing high-performance gas sensors that exhibit new
functions.
The present authors [149] used solvothermal self-assembly to
prepare pure and Cr-doped NiO hierarchical nanostructures. Ultrahigh selectivity and response to methyl benzenes such as xylene
and toluene were achieved using 1.15 at% Cr-doped NiO hierarchical nanostructures, while no signicant selectivity to xylene
or toluene were achieved using undoped NiO hierarchical nanostructures (Fig. 12). The enhanced response of the Cr-doped NiO
hierarchical nanostructures to the xylene and toluene gases was
attributed to the decrease in the concentration of holes in the

Cr-doped NiO due to doping NiO with trivalent Cr. The superior
selectivity of the Cr-doped NiO to methyl benzenes and minimal
cross-responses to benzene, HCHO, C2 H5 OH, and other interfering gases was explained by the catalytic oxidation of methyl group
by Cr components. These results indicate that properly designing aliovalent dopants that exhibit catalytic activity can enhance
not only the gas response of oxide semiconductor sensors by
electronically sensitizing the sensors but also the gas selectivity
of the sensors by chemically sensitizing them. It is noteworthy
that the selective detection of representative indoor pollutants
such as xylene and toluene with minimum interferences to other
gases, which had been a difcult task using conventional n-type
oxide semiconductor gas sensors, was successfully achieved by
Fig. 12. Responses of (a) pure NiO hierarchical nanostructures and (b) 1.15 at% Cr-doped NiO hierarchical nanostructures to 5 ppm o-xylene, toluene, benzene, formaldehyde,
and ethanol measured at 400 C, according to Ref. [149].
618
Fig. 14. (a) Gas sensors fabricated using CuO(p)/ZnO(n) heterocontact (b) IV characteristics, and (c) sensors fabricated using thin lm CuO/ZnO(n) heterojunctions, according
to Refs. [154156].
the synergetic combination of p-type sensing (NiO) and p-type

aliovalent dopant (CrO) materials with distinctive catalytic properties. This demonstrates that both a high degree of selectivity and
a high degree of sensitivity can be achieved using p-type oxide
semiconductors.
The present authors used solution synthesis to [104] prepare
undoped CuO nanosheets and CuO nanorods doped with 2.2 at%
Cr, and subsequently investigated the gas-detection characteristics of these nanostructures (Fig. 13). The response of the CuO
nanorods doped with 2.2 at% Cr to 100 ppm NO2 at 250 C was
very high (Ra /Rg = 134.2), while the cross-responses to C2 H5 OH,
NH3 , trimethylamine, C3 H8 , and CO remained low (Rg /Ra = 1.56.1)
(Fig. 13b). In contrast, the response of the pure CuO nanosheets
to 100 ppm NO2 was not only low (Ra /Rg = 5.6) but also comparable to or slightly higher than the cross-responses to other gases
(Rg /Ra = 1.25.1) (Fig. 13a). The markedly enhanced selectivity was
attributed to the catalytic function of the Cr component in promoting NO2 sensing. This example demonstrates again that doping an
oxide semiconductor with an aliovalent material that exhibits catalytic activity can simultaneously enhance both the response and
selectivity of sensors. It should be noted that not only reducing
gases but also oxidizing gases can be detected in a sensitive and
selective manner using p-type oxide semiconductors.
5. High-performance gas sensors using oxide pn junctions
The junctions between p- and n-type semiconductors provide
a range of valuable applications such as diodes, transistors, solar
cells, photo sensors, and light-emitting diodes [60,150152]. However, most studies to date have concentrated on devices fabricated
using doped-Si or compound semiconductors, and devices fabricated using oxide pn junctions have been barely investigated. To
date, there has been research on the design of high-performance
gas sensors fabricated using (1) longitudinal oxide pn junctions,
(2) nanocomposites sandwiched between p- and n-type oxide
semiconductor nanoparticles, and (3) 1-dimensional n-type oxide
semiconductors decorated with p-type oxide semiconductor nanoclusters for application as chemiresistors.
5.1. Gas sensors using longitudinal oxide pn junctions

Kawakami and Yanagida [153] suggested for the rst time
that humidity sensors could be prepared using the junction
between polycrystalline pellets of p-type Li-doped NiO and ntype ZnO. Further, it is been reported that not only the moisture
from humidity but also other gases including CO, H2 , and Cl2
could be measured under the direct current (DC)-bias of oxide
pn junctions such as CuO(p)/ZnO(n) [154160], SiC(p)/ZnO(n)
[161], La2 CuO4 (p)/ZnO(n) [162,163], and SrCu2 O3 (p)/ZnO(n) [164].
The asymmetric currentvoltage (IV) characteristics indicated
the formation of built-in potential near the pn junction, and
variation in the amount of current produced under forward or
reverse bias was used as a sensor signal when the sensor was
exposed to analyte gas. The adsorption of oxygen anions establishes the electrical coreshell structures in both n- and p-type
oxide semiconductors, and the congurations, thicknesses, and
electrical properties of the EDLs in n-type oxide semiconductors
and HALs in p-type oxide semiconductors depend on the density
of donors/acceptors and on the reaction between the oxide semiconductor and moisture and/or between the oxide semiconductor
and reducing/oxidizing gases. From this perspective, the change
in the IV characteristics of longitudinal pn junctions exposed
to oxidizing/reducing gases under DC-bias is attributed to the
variation in the built-in potential near the pn junction. Accordingly, the energy band diagram for the region near the junction
should be understood [165], and the p- and n-type oxide semiconductors should be carefully chosen by considering their work
functions, bandgaps, and electron afnities in order to fabricate
high-performance gas sensors from longitudinal oxide pn junctions.
The junctions formed between polished, sintered pellets of pand n-type oxides were used as sensors in the beginning stage
of research on gas sensors (Fig. 14a and b). Although the point
contacts between locally convex regions of p- and n-type oxide
semiconductors render the indiffusion of oxygen and analyte gas
near pn junctions through the crevices near the interfaces, it is difcult to reproduce and stabilize such sensors long term because the
619
Fig. 15. (a) Schematic illustration for alternatively driven metaloxide nanowires junction. Zn and Cu metal lms were selectively deposited by ebeam evaporator, followed
by the growth of nanowires on single substrate. (b) Schematic representation of a crossed-nanowire junction array platform and the corresponding SEM images. (c) Optical
Images of the nanowires junctions on single substrate. (d) Representative IV curves measured at room temperature, which show the typical nonlinear Schottky-like transport
behaviors. The 2 and 8 are 2 times and 8 times of original current, respectively. (e) Energy band diagram of each junction type through the overlapping nanowires. In nn
and pn junctions, Electrons pass over the barrier height, which is strongly dependent on the properties of the contact materials, whereas holes in pp junction ow through
the hole accumulation layer (the core (dark region) and shell (light region) means the bulk and surface, respectively).
contact area of pn junctions closely depends on the roughness

of the oxide semiconductor surface and the amount of pressure
applied to the oxide semiconductor in order to produce the point
contact. Further, producing the perfect heteroepitaxial interface
between n- and p-type oxide semiconductors is not advantageous
for obtaining a strong response to gases because oxygen is not
adsorbed and gases are not sensed at the interface. Thus, the
structures of gas sensors should be carefully designed considering
both the gas accessibility and reproducibility of the pn interface.
Indeed, Ushio et al. [154] used sputtering and photolithography to
pattern ZnO layers onto CuO lms and demonstrated that the patterned lms could be used as a humidity sensor that showed high
gas accessibility and reproducibility (Fig. 14c).
The p- and n-type oxide semiconductors in longitudinal oxide

pn junctions can show different afnities and reactivities to
oxygen and reducing gases. Thus, combining various p- and n-type
oxide semiconductors can be an effective strategy for selectively
detecting various gases. Vasiliev et al. [166] previously reported
that CuO(p)/SnO2 (n) thin-lm heterostructures showed asymmetric IV characteristics and strong response to H2 S. Devi et al.
[167] also previously reported that H2 S had been selectively and
sensitively detected in CuO(p)/SnO2 (n) heterocontacts. The high
response and selectivity to H2 S in CuO(p)/SnO2 (n) can be attributed
to the chemical afnity of CuO toward H2 S and converting from
p-type semiconducting CuO to metallic CuS upon exposure to H2 S.
Using an alternating current (AC) to measure gas concentrations
Fig. 16. Dynamic sensing transients of (a) pure ZnO(n) NWs, (b) Mn3 O4 (p)-decorated ZnO(n) NWs, (c) ZnO(n)-ZnMn2 O4 (p) coreshell NCs, and (d) Mn3 O4 (p) NWs to
100 ppm C2 H5 OH measured at 450 C, according to Ref. [53].
620
Fig. 17. Gas responses (Ra /Rg ) and air resistances (Ra ) of pure ZnO NWs and (a) NiOZnO NWs, (b) Cr2 O3 ZnO NWs, and (c) Mn3 O4 ZnO NWs to 100 ppm C2 H5 OH and
trimethylamine measured at various sensing temperatures, according to Refs. [53,208,209].
has also been suggested as an alternative method of developing

selective gas sensors. Hikita et al. [168,169] measured the complex
impedance of DC-biased CuO(p)/ZnO(n) heterocontacts under
various atmospheres. They reported that the reactance (i.e., the
imaginary component of complex impedance) plotted as a function
of log(AC frequency) showed a minimum peak and that the absolute
reactance and peak frequency varied differently when the heterocontacts were exposed to air, CO, and H2 and when the DC bias was
varied. Thus, CO and H2 could be selectively detected by choosing
a proper AC frequency for measuring reactance under a xed
DC bias.
Single crystalline oxide nanowires (NWs) have recently
attracted attention as materials for fabricating gas sensors because
such materials show high surface-area-to-volume ratios and excellent crystallinities [170]. Park et al. [171] recently reported that the
air-bridge-structured junction between the single crystalline oxide
NWs of n-type ZnO and p-type CuO (diameters: 30 nm) could be
fabricated by growing long ZnO and CuO NWs (length: 10 m) on
Zn and Cu lms (the gap between Zn and Cu: 5 m) (Fig. 15ac).
The IV characteristics of the CuO(p)/ZnO(n) heterocontacts were
asymmetric, while those of the ZnO(n)/ZnO(n) and CuO(p)/CuO(p)
heterocontacts were symmetric (Fig. 15d). This nding clearly supports that the built-in potential had been established near the pn
junction (Fig. 15e) and that the air-bridge-structured oxide pn
junction could be used to fabricate gas sensors. Although the NWbased pn junction showed high gas accessibility at the junction,
it showed low current levels during measurement because of the
small contact area between the p- and n-type oxide NWs.
5.2. Gas sensors using nanocomposites between p- and n-type
oxide semiconductors
Nanocomposites between p- and n-type oxide semiconductors,
in contrast to longitudinal pn junctions, do not exhibit asymmetric IV characteristics because many pn nanojunctions are serially
and randomly connected. However, the overall gas response of
a sensor can be signicantly enhanced by properly designing
nanocomposites when there is a high degree of chemiresistive variation at pn nanojunctions.
Conduction along nanocomposites between p- and n-type oxide
semiconductor nanoparticles depends on the concentration, size,
and dispersion of the two phases. If a small number of p-type
Fig. 18. Dynamic C2 H5 OH-sensing transient for NiO-functionalized SnO2 hollow spheres measured at 450 C, according to Ref. [62].
621
Fig. 19. Gas-sensing transients for (a) pure-SnO2 , (b) 0.64 wt% NiO-loaded SnO2 , and (c) 1.27 wt% NiO-loaded SnO2 hierarchical spheres in dry and 25% relative humidity
atmospheres to 50 ppm CO measured at 400 C, according to Ref. [61].
oxide nanoparticles are discretely dispersed throughout the n-type

nanoparticles, the variation in the chemiresistivity of the sensor
will be dominated by the n-type nanoparticles located at the pn
and nn interfaces. However, if the p-type nanoparticles are percolated throughout the n-type nanoparticles, parallel competition
along p- and n-channels will determine the conduction of the sensor material. Thus, the resistance of n-type oxide semiconductors
initially increases when a small concentration of p-type oxide semiconductors is loaded by establishing a resistive pn junction. As the
concentration of p-type oxide semiconductors dispersed throughout the n-type nanoparticles increases, the resistance shows the
maximum and then decrease due to the formation of percolative
conduction path along p-type nanoparticles. These ndings are
consistent with previous reports that the maximum resistances
of Co3 O4 (p)SnO2 (n) [172] and CuO(p)ZnO(n) [173,174] composites are higher than those of their pure n- or p-type counterparts.
From this perspective, the concentration, size, and dispersion of
p-type additive materials are key parameters in determining the
conduction path and gas-sensing mechanism of sensor materials.
The change in the size of particles in n-type sensor materials and
the variation in pore size or pore-size distributions due to loading
p-type oxide additives should also be taken into account as parameters that can signicantly affect the gas sensing characteristics.
H2 S-selective sensors fabricated using CuO(p)-loaded n-type
oxide semiconductors such as SnO2 [175196], ZnO [197200],
MoO3 [201], and ZnSnO3 [202] are representative examples of
using nanocomposites between p- and n-type nanoparticles to
design high-performance gas sensors. The resistances of such
sensors are high in air because of the pn nanojunctions in the
sensors. When such sensors are exposed to H2 S, the surfaces
of semiconducting CuO (which shows a high chemical afnity
for H2 S) are converted into metallic CuS, which decreases or
nullies the built-in potential near pn junctions and signicantly
decreases the resistance of the sensors [176,197]. Accordingly, the
highly selective detection of H2 S in CuO-loaded n-type oxide semiconductor gas detectors is explained by the change in energy-band
structures due to the p-type CuO semiconductor converting into
metallic CuS near the junctions.
5.3. Gas sensors using 1-dimensional n-type oxide
semiconductors decorated with p-type oxide nanoclusters
The high surface-area-to-volume ratio and good crystallinity
of 1-dimensional (1-D) oxide nanostructures such as NWs,
nanotubes, and nanorods are advantageous for fabricating sensors that show long-term stability and a strong response to gases
[3,170,203]. However, the single crystalline 1-D NWs grown using
the vaporliquidsolid (VLS) mechanism are generally thicker than
70 nm [204206], while the EDL near the surface of n-type oxide
semiconductor NWs is thinner than 510 nm [207]. Thus, it is challenging to fabricate gas sensors that show a strong response to gases
by fully depleting the electrons in NWs.
The present authors [53] prepared ZnO(n) NWs, Mn3 O4 (p)decorated ZnO(n) NWs, ZnO(n)ZnMn2 O4 (p) coreshell
nanocables (NCs), and pure Mn3 O4 (p) NWs by controlling the transformation of ZnO NWs into Mn3 O4 NWs in the vapor phase (Fig. 16).
The pure and Mn3 O4 (p)-decorated ZnO NWs showed n-type gassensing characteristics (Fig. 16a and b), while ZnO(n)ZnMn2 O4 (p)
coreshell NCs and pure Mn3 O4 (p) NWs showed p-type
gas-sensing characteristics (Fig. 16c and d), indicating that
the conduction occurs along the networks of n-type ZnO NWs in
Mn3 O4 (p)-decorated ZnO NWs and is dominated by ZnMn2 O4 (p)
shell layers in ZnO(n)ZnMn2 O4 (p) coreshell NCs. The relatively
low gas responses shown in Fig. 16c and d are attributed to the distinctive gas-sensing mechanism of p-type oxide semiconductors.
However, the increase in the gas response (Ra /Rg ) from 7.2 to 30.8
achieved simply by decorating the 1-dimensional n-type oxide
semiconductors with discrete p-type oxide nanoclusters is unusual
and interesting. Decorating the sensor with Mn3 O4 nanoclusters
increased its resistance in air by 2 orders of magnitude (Fig. 17c),
indicating that the EDL under Mn3 O4 nanocluster had radially
extended in the direction of the ZnO NWs (see schematics shown
in right and lower part of Fig. 2), consequently decreasing the
cross-sectional area of the core n-channel in the ZnO NWs.
We also found that decorating n-type ZnO NWs with various
other p-type nanoclusters such as NiO, and Cr2 O3 signicantly
enhanced the gas response of the NWs and that the enhanced
gas response was always accompanied by a marked increase (i.e.,
2 orders of magnitude) in sensor resistance (Fig. 17a and b).
The increases in gas response typically achieved by decorating ntype ZnO NWs with NiO, Cr2 O3 , and Mn3 O4 are shown in Fig. 17
[53,208,209]. Therefore, decorating n-type oxide NW networks
with p-type nanoclusters is a powerful strategy of enhancing the
response of n-type oxide NW-based materials to various gases.
Moreover, decorating n-type oxide NW-based materials with ptype nanoclusters that exhibit catalytic activity for a specic gas
can enhance not only the gas response but also the gas selectivity of
the sensor materials. Hwang et al. [210] used the VLS mechanism to
622
grow SnO2 NWs and chemically coated their surface with a discrete
layer of CuO. Shao et al. [211] also used two-step chemical vapor
deposition to prepare CuO(particle)SnO2 (NW) heterostructures.
The authors of these two studies reported that decorating the surfaces of the SnO2 NWs with p-type CuO nanoclusters signicantly
enhanced the selectivity and response of the NWs to H2 S. One of the
present authors [209] previously reported that decorating n-type
ZnO NWs with p-type Cr2 O3 nanoclusters signicantly enhanced
the selectivity and response of the NWs to trimethylamine because
of the synergetic effects of promoting the adsorption of trimethylamine on the surface of the Cr2 O3 nanoclusters and extending the
EDL under them.
6. High-performance gas sensors using

p-type-oxide-semiconductor-loaded n-type oxide
semiconductors
6.1. Enhancement of recovery speed by loading NiO onto SnO2
hollow spheres
The rapid response and recovery of gas sensors are essential
for quickly detecting and monitoring levels of toxic, explosive, and
dangerous gases in real time [7,11]. The kinetics of gas-sensing
and recovery should be understood in the context of a gas-sensing
mechanism. Using n-type oxide semiconductors to detect reducing gases consists of a series of steps including the in-diffusion
of an analyte gas toward the oxide surface, the oxidation of the
reducing gas by reacting with oxygen anions on the oxide surface,
and the injection of electrons into the semiconducting material.
The gas-sensing reaction can occur within a few seconds when
the sensor materials are sufciently dispersed to guarantee fast
diffusion of gas and when the sensing temperature is sufciently
high to induce a rapid reaction between the analyte gas and the
oxygen anions [109]. However, such rapidly responding, porous ntype sensor materials often show prolonged recovery times (e.g.,
303000 s) at the same temperature. The recovery reaction consists of the in-diffusion of oxygen gas to the sensor surface and
subsequent surface reactions such as the adsorption, dissociation,
and ionization of the oxygen. The surface reactions that form the
oxygen anions on the surface of the sensor material are sluggish and comprise the rate-determining step when a gas rapidly
diffuses.
The present authors [62] uniformly coated a Sn-precursor onto
Ni spheres, heated the Ni spheres to partially oxidize them and
to convert the Sn-precursor into SnO2 , dissolved the Ni metal
cores of the spheres, and subsequently heated the hollow spheres
to prepare SnO2 hollow spheres whose inner walls were decorated with NiO nanoparticles. The NiO-decorated SnO2 hollow
spheres showed ultrarapid recovery (i.e., 90% recovery in <5 s)
(Fig. 18a). Commercially produced SnO2 nanoparticles exposed
to 20100 ppm C2 H5 OH showed 90% recovery after a very long
time (i.e., 124708 s), and NiO loading decreased the recovery time
of the commercial SnO2 spheres to <30 s. Wang et al. [212] also
reported that NiOSnO2 hollow spheres showed very rapid recovery (90% recovery = 4 s) from the sensing of 20 ppm NH3 at 300 C.
Considering that abundant oxygen is adsorbed in NiO, transferring oxygen anions or electrons from the NiO to the adjacent SnO2
has been suggested as the probable reason for the rapid recovery of the sensor fabricated using NiO-decorated SnO2 hollow
spheres (Fig. 18b). It is noteworthy that the concentration of oxygen adsorbed on p-type oxide semiconductors is generally higher
than that on n-type oxide semiconductors. Thus, loading p-type
oxide materials onto n-type oxide semiconductor gas sensors can
enhance the recovery kinetics by transferring adsorbed oxygens or
electrons from p- to n-type oxide semiconductors.
6.2. Humidity-independent gas sensors using NiO-loaded SnO2

nanostructures
Oxide semiconductors react with ambient moisture as well as
analyte gas [55,213216], which hampers the reliable operation of
gas sensors. Ambient humidity signicantly varies according variations in weather, climate, temperature, and season. In addition,
the concentration of moisture in the atmosphere ranges from 6000
to 12,000 ppm (measured at 1 atm) at 25 C and 3080% relative
humidity (RH), which is signicantly higher than the typical concentration of moisture in target analyte gases (i.e., 1100 ppm).
From the perspective of maintaining reliably operating gas sensors,
it is very important to eliminate or decrease the dependence of the
signal of oxide semiconductor gas sensors on humidity. Moreover,
oxide semiconductor gas sensors must be able to reliably detect
trace concentrations of acetone [217,218], NH3 [219], NO [220],
and CO [221] even under very humid (typically RH >80%) exhaled
breath of patients in order to use oxide semiconductor gas sensors
to diagnose various diseases such as diabetes, lung cancer, asthma,
and bronchiectasia.
The present authors [61] prepared pure SnO2 hierarchical
nanostructures and 0.641.27 wt% NiO-loaded SnO2 hierarchical
nanostructures and measured their CO-detection characteristics
in dry and humid (i.e., 25% RH) atmospheres (Fig. 19). The
gas-detection characteristics of the pure SnO2 hierarchical nanostructures showed signicant variation depending on whether the
nanostructures were placed in a dry or humid atmosphere. For
example, (1) the sensor resistance was lower in the humid atmosphere than in the dry one; (2) the response was slower in the
humid atmosphere than in the dry one; (3) the recovery was
slower in the humid atmosphere than in the dry one; and (4) the
response of the sensor to CO deteriorated in the humid atmosphere (Fig. 19a). The rapid recovery characteristics achieved by
loading SnO2 with NiO, as explained in Section 6.1 were retested
using 0.64 and 1.27 wt% NiO-loaded SnO2 hierarchical nanostructures (Fig. 19b and c). Except for the sensor resistance in air, the
response and recovery speeds and the gas response of the 0.64 wt%
NiO-loaded SnO2 hierarchical nanostructures placed in the 25%
RH atmosphere were similar to those of the same nanostructures
placed in the dry atmosphere. All the gas-detection characteristics of the 1.27 wt% NiO-loaded SnO2 hierarchical nanostructures
placed in the 25% RH atmosphere were similar to those of the same
nanostructures placed in the dry atmosphere. These results clearly
show that doping or loading SnO2 hierarchical nanostructures with
NiO is very effective not only for fabricating rapid-recovery sensors but also for decreasing the humidity dependences of all the
gas sensing characteristics such as sensor resistance, gas response,
and response/recovery speed to negligible levels.
We [222] also reported that gas-detection characteristics such
as the CO response, response and recovery times, and sensor
resistance in air for NiO-doped SnO2 nanoparticles could remain
constant over a wide range of relative humidities (i.e., RH = 080%)
(Fig. 20), which is further evidence that the NiO additive plays
the key role in developing humidity-independent gas sensors and
that NiO-loaded SnO2 sensors can be used to analyze exhaled
breath in order to diagnose diseases. The results of the operando
diffuse-reectance Fourier transform infrared (IR) spectroscopy
suggest that the NiO blocks the interaction between the SnO2
surface and moisture. Considering the large amount of moisture in the atmosphere, the humidity-independent gas-sensing
behavior of the NiO-loaded SnO2 sensor reects the strong and
regenerative interaction between the discretely congured NiO
nanoparticles and the moisture in the atmosphere. And this is
feasible considering that a number of transition metal oxides
readily form complexes with H2 O and NH3 ligands that have lone
pair(s) of electrons. Thus, the distinctive oxygen adsorption at the
623
Fig. 20. Gas-sensing characteristics of pure (circle), 0.4 at% (triangle), 1.0 at% (square), and 2.0 at% (diamond) Ni-loaded SnO2 placed in dry and in 2580% RH atmospheres
(gas: 50 ppm CO) (a) Gas response (Ra /Rg ), (b) 90% response time (tres ), (c) 90% recovery time (trecov ), (d) resistance in air (Ra ) measured at 400 C.
NiO surface and the chemical afnity between the NiO surface
and the moisture in the atmosphere seem to play the key role in
determining humidity-independent gas-sensing characteristics.
Therefore, p-type oxide semiconductors with high chemical
afnity to moisture are good candidates for possibly decreasing
the humidity-dependence of the gas-detection characteristics of
n-type oxide semiconductor gas sensors.
7. Conclusions
The oxygen adsorptions, the formation of electrical coreshell
structures, conduction mechanisms, catalytic activities, and the
interactions with humidity of p-type oxide semiconductors are
signicantly different from those of n-type oxide semiconductors,
which can be used to fabricate gas sensors that exhibit various novel
functionalities. Conduction occurs along the hole-accumulation
layer near the surface where oxygen anions are adsorbed in ptype oxide semiconductor gas sensors; thus, the concentration
of holes in the hole-accumulation layer decreases when p-type
oxide semiconductor gas sensors are exposed to reducing gases,
often leading to relatively weak responses to such gases. However, the responses of p-type oxide semiconductor gas sensors can
be sufciently enhanced using aliovalent materials (i.e., electronic
sensitization), by catalytically promoting gas detection (i.e., chemical sensitization), and by decreasing the size of the nanostructure
so that p-type oxide semiconductor gas sensors can be used for
practical applications. In addition, the selectivity of p-type oxide
semiconductor gas sensors can be further tuned by doping or loading of catalysts that can promote the reaction between the sensor
and a specic gas.
Longitudinal oxide pn junctions that show asymmetric IV
characteristics can be used as gas sensors. Gas-sensing characteristics such as the gas response and selectivity can be tuned by
combining various p- and n-type oxide semiconductors, designing
contact congurations, changing bias voltage, and using AC current
with longitudinal oxide pn junctions. Nanocomposite materials
between p- and n-type oxide nanostructures can be also used to
enhance the response and selectivity. In particular, highly selective
and sensitive H2 S sensors can be fabricated using p-type CuOloaded n-type oxide semiconductors by changing the resistive pn
junctions between the CuO and the n-type oxide semiconductors
into the conducting hetero-junctions between CuS and the n-type
oxide semiconductors upon exposure to H2 S. Moreover, decorating
n-type oxide nanostructures with discretely congured p-type
oxide nanoclusters is a very effective method of enhancing the
responses of 1-dimensional n-type oxide nanostructures to various
gases.
P-type oxide semiconductors such as NiO, CuO, Co3 O4 , Cr2 O3 ,
and Mn3 O4 are excellent catalysts that can be used to tune or
promote the oxidation/reduction of various volatile organic compounds. Thus, not only undoped p-type oxide semiconductor gas
sensors but also n-type oxide semiconductor gas sensors loaded
with p-type oxide semiconductor additives can be used to fabricate highly selective gas sensors. Moreover, rapid recovering
and humidity-independent gas sensors can be fabricated using
p-type oxide semiconductors or p-type oxide semiconductor additives because of distinctive oxygen adsorption and interaction with
moisture of p-type oxide semiconductors.
The gas responses of p-type oxide semiconductors, which have
been regarded as lower than those of n-type oxide semiconductors, can be sufciently enhanced through electronic and chemical
sensitization so that p-type oxide semiconductor sensors can
be used for practical applications. The various congurations of
oxide pn junctions including longitudinal junctions, multijunctions in nanocomposites, and 1-D n-nanostructures decorated with
p-nanoclusters provide new direction in fabricating gas sensors. pType oxide additives can decrease the humidity dependence and
signicantly increase the recovery speed of n-type oxide semiconductor gas sensors. Therefore, p-type oxide semiconductors
that show distinctive catalytic activities, surface reactivities, and
electrical properties are promising materials for fabricating highperformance gas sensors and are excellent additives for enhancing
the performance of gas sensors.
Acknowledgment
This work was supported by the National Research Foundation
of Korea (NRF) grant funded by the Korea Government (MEST) (No.
2013R1A2A1A01006545).
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Biographies
Hyo-Joong Kim studied Materials Science and Engineering and received his B.S. and
M.S. degrees in 2009 and 2011, at Korea University in Korea. He is currently doing
his Ph.D. at Korea University. His research interest is the design of high-performance
p-type oxide semiconductor gas sensors.
Jong-Heun Lee joined the Department of Materials Science and Engineering at Korea
University as an associate professor in 2003 and is currently a professor there. He
received his B.S., M.S., and Ph.D. degrees from Seoul National University in 1987,
1989, and 1993. Between 1993 and 1999, he developed automotive air-fuel-ratio
sensors at the Samsung Advanced Institute of Technology. He was a fellow of the
Science and Technology Agency (STA) of Japan at the National Institute for Research
in Inorganic Materials (currently the National Institute for Materials Science (NIMS),
Japan) from 1999 to 2000 and was a research professor at Seoul National University from 2000 to 2003. His current research interests include chemical sensors,
functional nanostructures, and solid oxide electrolytes.

Highly Sensitive and Selective Gas Sensors Using P-Type Oxide

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Sensors and Actuators B 192 (2014) 607627

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Sensors and Actuators B: Chemical

Highly sensitive and selective gas sensors using p-type oxide

be used to design high-performance gas sensors that show low

amount of oxygen adsorbed in 16 metal oxides by measuring the

Particle size (nm)

2.3. Conduction and gas-sensing mechanisms of n- and p-type

core, which decreases the sensor resistance proportional to the

material through the oxidation reaction between the reducing gas

This insightful equation clearly shows that designing highly

oxide semiconductors were the most abundant in the literature.

Fig. 5. Gas-sensing mechanism and equivalent circuit of n-type oxide semiconductors.

semiconductor gas sensors. The gas responses of p-type oxide

a large or small cube whose edges are 100 or 20 nm long were

area between particles, indicating that the interparticle connection

when very small nanostructures are used, because of the distinctive

Fe2 O3 2FeNi + 2OX

enhanced to 6.7 times by loading the nanostructures with Au

SiO2 NiO nanoparticles

organic compounds such as CO, NH3 , C2 H6 , CH3 CHO, C6 H6 , and

attributed to the decrease in the concentration of holes in the

the synergetic combination of p-type sensing (NiO) and p-type

5.1. Gas sensors using longitudinal oxide pn junctions

contact area of pn junctions closely depends on the roughness

The p- and n-type oxide semiconductors in longitudinal oxide

has also been suggested as an alternative method of developing

oxide nanoparticles are discretely dispersed throughout the n-type

6. High-performance gas sensors using

6.2. Humidity-independent gas sensors using NiO-loaded SnO2

[28] I. Castro-Hurtado, C. Malag, S. Morandi, N. Prez, G.G. Mandayo, E. Castan,

[155] Y. Ushio, M. Miyayama, H. Yanagida, Effect of interface states on gas-sensing

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